Contact decolorization



portant, as it Patented Sept. 1, 5.942

2,294,779 CON'EAGT DECOLOBIZATION Iulius n, Corporation, K linois No Drawing.

Chicago, 111., Chicago, 111.,

assignor to 'Velsicoi a corporation of 11- Application November 22, 1939, Serial No. 305,676

'8 Claims. (01. 196-1431) This invention relates to the decolorization in the liquid phase of water-insoluble, naphtha-soluble substances, such as animal, vegetable, ma-

rine and mineral oils, waxes and resins both of ties, and are further undesirable because of their friability and their naturally occurring ratios of aluminum to silicon. At best, their porosities and strength can be altered comparatively slightly.

As opposed to these defects, synthetic aluminosilicates may be prepared in practically any degree of purity, and their strength, porosities and aluminum-silicon ratios may be varied within wide limits. These advantages are extremely imlytic, porous aluminosilicates best suited for each specific requirement.

The degree of porosity is of primary importance in the production and use of synthetic aluminosilicates. In the'case of decolorizing agents, only those synthetic alumina silicates appear as to permit ready entrance of the tinctorial bodies. This porosity is reflected generally in the apparent density of the catalyst, the lower the apparent density the greater being the porosity. Tests which I have made indicate that the maximum apparent density of an active synthetic aluminum silicate should be less than 60, the apparent density being defined as the weight in pounds of a cubic foot of unpacked material which is dry to the touch and has a screen size between 8 and 80 mesh, over 50% of which being of a. screen size between and 60 mesh.

Silicates may be precipitated as gels from an alkaline, neutral or acid solution. Alumino-silicates precipitated in an alkaline solution usually possess pronounced base-exchange, or, zeolite properties. The neutral and acidic gels show the is thus poss'ble to prepare catano-silicates either same property to a lesser must be freed degree. Such silicates of water-soluble alkali before they will function as color adsorbents. This may be accomplished, for example, by washing or boiling the granular silicate with an aqueous 1 solution of a salt of a polyvalent metallic ion (said ion comprising the cation of the salt) until all excessive alkali has been neutralized. The desired results may also be obtained by washing the aluminosilicate with an aqueous solution of an ammonium salt, washing out the excess of the salt with water, and heating the treated silicate to break down the'ammonium aluminosilicate complex and drive off the liberated ammonia. Very mildly acid washings may also be used to remove replaceable alkali. As a pre-treatment in preparing synthetic zeolites to sorbents, it is well first to Wash away with water as much alkali and occluded salts as conveniently possible.

The porosity of the alumino-silicate gels may be increased by the addition of water-soluble foreign materials prior to precipitation. After the gel has set, these water-soluble materials may be leached away, thus leaving minute voids increase the surface-and hence the porosity-of the also be created by the addition of substances, such as ammonium nitrite, to the gel-forming solutions, which substances tend to gasify on the application of mild heat. This heat may then be applied during the drying and setting period of the gel.

The strength of a synthetic aluminosilicate depends not only on its method of preparation, but also on the ratio of silicia to alumina. Other things being equal, the rule is that the greater the percentage of silica in the gel, the stronger and more rigid it will be. However, when the ratio by weight of alumina (A1203) to silica (SiOz) falls below 1 to 25, the quantity of alumina present is so reduced that the gel ceases for practical purposes to be sufficiently active for the uses herein contemplated. On' the other hand, when the ratio by weight of alumina to silica rises above equality, the resulting gel is too frangible for ordinary commercial use. An alumina-silica ratio of 1 to 6 appears quite satisfactory for most purposes herein mentioned.

Oils may be decolorized with synthetic alumiby the familiar methods of contact filtration or percolation. adsorbent dust of -300 mesh fineness (occasionally coarser material is used) is combined with the oil to form a slurry. This is generally function as adfinal dried gel. Voids may I In the former,

2 2,294,779 V .7 heated to 100-600 l depending on the viscosity and resins, the step which comprises subjecting and gene nature of the oil. and kept at these said substances in the liquid phase to the adtemperatures for carrying times up to three or sorptive action of a solid, porous, homogeneous. four hours. A commonly used temperature for synthetic alumina-silicate gel from which all many oils is 300 F. withahalf hour contact replaceable and water-soluble alkali has metime. viously been removed.

After appropriate cooling, the oil slurry is then 2. In the decolorization treatment of naphtha piped to a filter press or vacuum filter, wherethe soluble, water-insoluble hydrocarbon oils, waxes separation of oil from spent adsorbent is elected. and resins the step which comprises subjecting The adsorbent cake maybe treated with naphtha 0 said substances in the liquid phase to the adto wash out residual oil held by the cake. Under sorptive action of a solid, poro homogeneous, proper conditions, the adsorbent used in contact synthetic alumino-silicate gel from which all refiltration may be reactivated by ignition' alplaceable and water-soluble alkali has previously though the general practice is to discard the n removed, said aluminium silicate containfine adsorbent It may alsobe treated with strong ing a weight ratio of alumina to silica between oxidizing agents, such as hot diluted hydrogen approximately 1 1 to 1:25 and being much more peroxide or potassium permanganate solution stable than natur occurring alumina-silicates which oxidize the impurities adhering to the adagainst loss of activity upon ep a ed ca c n n sorbent, and thus reactivate it. 1 V 3 In the decolorization treatment of naphtha- In the treatment of 011 by percolation th 11 soluble, water-insoluble waxes, resins and the are passed through a bed of the adsorbent, which ke hydr ca b su stan s. th st p wh ch will vary from about 8 to 100 mesh in size A 1 comprises subjecting said substances in the liqcontact filtration, the temperature of the oil and phase to the adso ptive a ti n of id, the time of contact will depend on such factors P h m n us, s nth ic alinnino-silicate a th viscosity of th ll, it tendency t l m gel from which all replaceable and water-soluble pose, the nature of the colored bodies to be realkali s P i y e n removed, which has moved, and economic considerations Because of been l n d n air. its size, the spent adsorbent may be readily re-. 4. In the decolorization treatment of naphthaactivated by calcining at about l200 F in a cur- Solll e hydrocarbons, the p whi h comprises rent of air Experiments indicate that after a ting said hydrocarbons in the liquid ph primary calcining the synthetic aluminosilicates to the ads a t n f a solid p us, h m may be recalcined as often as desired without geneous synthetic al min -s he gel m iou reduction in d olorizm and/o polymerwhic all replaceable and water-soluble alkali izing activity, provided the adsorbents are not has P v sly een removed. sintered in the calcining, However, synthetic 5. In the dEOOIOI'iZatiOD treatment of mineral aluminosilicates appear to be much more stable oils, the step which p ises subject said than the nationally occurring aluminosilicates oils in the q d P as to the ads pt ve action in this respect. 7 of a solid, porous, homogeneous, synthetic It will also be seen that an adaptation of the alumino-silicate gel from which all r placeable percolation method may b utilized in t 40 and water-soluble alkah has previously been recolorization and filtering of automobile lubricatmoved. ing oils during operation of the motor vehicle, by v 6. In the decolorization treatment of lubricatusing a filter cell containing my synthetic alum1- o l fraotio of hydrocarbon oils, the step num silicate adsorbent and continuously by pas which comprises subjecting said fraction in the l th h 11; oil fpqm t crank, s of t liquid phase to the adsorptive action of a solid, automobile. porous, homogeneous, synthetic alumino-sllicate T decolorization ofi fats andfwaxes' gel from which all replaceable and water-soluble may be accomplished either by treating them in a, alkali has previo s y been m v molten condition in the aforementioned manners, In the decolorization m nt of hydroor preferably by first dissolving them in an appron r ns, the step which comprises subJectpriate hydrocarbon solvent, such as petroleum 8 e resins n e q id phase to the adnaphtha In order to prevent the naphtha from ve action f a solid, porous, homogeneous, evaporating, it may be necessary to carry out the synthetic alumino-silicate gel from which all decolorizmg treatment under super af;mospheric l replaceable and water-soluble alkali has prepressures e I viously been removed.

Examples of oils amenable-to adsorptive de- 8. In the decolorization and filtering of autocolorization are Mid-Continent lubricating oil mobile lubricating hydrocarbon o s d ring the fractions, crude cottonseed oil and crude neats operation of the motor Vehicle. the p whl h foot n 5, consists of passing a portion of said oil con- Examples of decolorizable solids are dark tinuously through 8 bed of granular P r s varieties of rosin, coumarone-indene resins and sorbent comprislng solid Porous, homogeneous, petroleum resilm synthetic alumino-silicate gel from which all re- 1 l in' as my i ti placeable and water-soluble alkah has previous- 1. In the decolorization treatment of naphtha-f v been m v soluble, water-insoluble hydrocarbon substances ULIUS HYMAN.

chosen from the class consisting of oils, waxes 

